Optical absorption studies of copper phthalocyanine thin films

The optical absorption of thermally evaporated copper phthalocyanine (CuPc) was studied in the UV-VIS-NIR region. The absorption spectra recorded in the UV-VIS region show two well-defined absorption bands of the phthalocyanine molecules, namely, the Soret (B) and the Q-band . The Q-band shows its characteristic splitting (Davydov splitting) of the main absorption peak in the metal phthalocyanine correlates with the relative tendencies of the metal to out-of-plane bonding. Some of the important spectral characteristics such as the molar extinction coefficient (ε_molar), the oscillator strength (f), the electric dipole strength (q²) and absorption half-bandwidth (Δλ) of the principle optical transitions were evaluated. The analysis of the spectral behavior of the absorption coefficient α in the absorption region revealed two indirect allowed transitions with corresponding energies 2.95±0.03 and 1.55±0.02 eV.The spectra of the infrared absorption allow characterization of vibration modes for the powder, as-deposited material and thin films of CuPc annealed at 423 K for two hours. Discussion of the obtained results and their comparison with the previous published data are also given.     

Optical recording using hydrogen phthalocyanine thin films

Vacuum sublimed thin films of the blue dye hydrogen phthalocyanine (H₂Pc) were incorporated into various optical recording structures. The dye was shown to be thermally, hydrolytically, and oxidatively stable. In all cases, the writing mechanisms are dependent on the sublimation of H₂Pc. Several recording structures which take advantage of the sublimation property of H₂Pc are demonstrated, including pit forming and bubble forming media. These H₂Pc-based optical recording structures show very high optical contrast and low writing threshold energies. In addition, very thin films (50–75Å) of H₂Pc were incorporated into a tellurium-based medium, which significantly enhanced the writing contrast observed in that medium.     

Optical characterization of thin thermal oxide films on copper by ellipsometry

A complete optical characterization in the visible region of thin copper oxide films has been performed by ellipsometry. Copper oxide films of various thicknesses were grown on thick copper films by low temperature thermal oxidation at 125 °C in air for different time intervals. The thickness and optical constants of the copper oxide films were determined in the visible region by ellipsometric measurements. It was found that a linear time law is valid for the oxide growth in air at 125 °C. The spectral behaviour of the optical constants and the value of the band gap in the oxide films determined by ellipsometry in this study are in agreement with the behaviour of those of Cu₂O, which have been obtained elsewhere through reflectance and transmittance methods. The band gap of copper oxide, determined from the spectral behaviour of the absorption coefficient was about 2 eV, which is the generally accepted value for Cu₂O. It was therefore concluded that the oxide composition of the surface film grown on copper is in the form of Cu₂O (cuprous oxide). It was also shown that the reflectance spectra of the copper oxide–copper structures exhibit behaviour expected from a single layer antireflection coating of Cu₂O on Cu. Received: 19 July 2001 / Accepted: 27 July 2001 / Published online: 17 October 2001     

Luminescence of phthalocyanine thin films

The near-IR luminescence in thin films of metal-free phthalocyanine and phthalocyanine complexes is investigated at room temperature. It is shown that the intensity of the luminescence peaks depends on the polymorphic modification and the structure of the complexes, whereas the peak positions remain virtually unchanged.     

Optical properties of zinc phthalocyanine thin films prepared by pulsed laser deposition

ZnPc thin films were prepared by pulsed laser deposition (KrF laser, λ = 248 nm, τ = 5 ns, f = 50 Hz) on suprasil substrates in vacuum. Optical properties in UV–Vis spectral region were analyzed as functions of laser fluence from 40 to 100 mJ/cm² by spectrophotometric and spectral ellipsometry measurements. The spectral ellipsometry data were treated using a three-layer model (substrate, film, roughness). The best results of data fitting were obtained when Q band was characterized by two Lorentz oscillators, while two Gaussian oscillators were used for B and C band fitting. We derived the band gap using Tauc plot considering ZnPc a direct band gap semiconductor. The band gap values were found decreasing from 3.13 to 3.09 eV with increasing laser fluence, which might be related with formation of trapping sites at higher fluence.     

Preparation and characterization of thermally evaporated titanium phthalocyanine dichloride thin films

Titanium phthalocyanine dichloride (TiPcCl₂) thin films are prepared on glass substrates by vacuum-sublimation technique. The optical constants of thin films are obtained by means of thin film spectrophotometry. Planar structures for the study of electrical properties are fabricated with TiPcCl₂ as active layer and silver as the contact electrodes. The effects of post-deposition annealing on the optical band gap have been studied. The optical transition is found to be direct allowed in nature. The invariance in the optical band gap shows the thermal stability of the material. The activation energies are determined using the Arrhenius plots between electrical conductivity and inverse temperature. The variation in activation energy with post-deposition annealing is investigated. The unit cell dimensions of TiPcCl₂ thin films are also determined by indexing the powder diffraction data. The variations of the surface morphology and grain size with annealing have also been studied.     

Electronic properties of the space charge layer of the copper phthalocyanine thin films

Photoemission Yield Spectroscopy (PYS) has been used in studies of the electronic properties of the space charge layer of UHV annealed copper phthalocyanine (CuPc) thin films. The work functionφ, ionization energyΦ, absolute band bendingeV _s and surface electron affinityX _s is determined. Moreover, two filled electronic state bands localized in the band gap are observed. Their origin is briefly discussed.     

酞菁铜衍生物在酞菁酮—氧化铁纳米粒子交替LB膜中的分子取向

通过Langmuir-Blodett技术制备了酞菁酮－氧化铁纳米粒子交替LB膜,利用偏振紫外－可见光谱对酞菁铜衍生物在不同制膜条件下所制得的交替膜中的分子取向进行了研究。结果表明,在同一氧化铁溶胶亚相中,随着表面压的增大,或在相同的表面压下,随着亚相中氧化铁浓度的减小,酞菁铜分子在其复合LB膜中倾斜程度变大。     

Twin—layer films of copper phthalocyanine and amorphous titanyl or vanadyl phthalocyanine

Metallophthalocyanine (MPc) twin-layer thin films on glass substrates, consisting of copper phthalocyanine (CuPc) overlayer and amorphous vanadyl phthalocyanine (VOPc) as well as titanyl phthalocyanine (TiOPc) buffers, were found to have different gas sensing characteristics. These twin-layer thin films were studied using x-ray photoemission spectroscopy. Photoelectrons of either V or Ti core levels were found to be present at the surface, indicating the existence of possible molecular migrations. The stability of the twin-layers under thermal annealing up to a maximum temperature of 250℃ and low-energy Ar ion bombardment was also examined and compared with that of CuPc directly grown on the substrates. We concluded that the twin-layer structures were thermally fairly stable. Ar ion bombardment, however, caused substantial damage to the Pc ligands and a reduction of the valence state of the central Cu atoms.     

Persistence in photoconductivity and optical property of nanostructured copper (II) phthalocyanine thin films

The optical and photoconductive properties of nanostructured copper (II) phthalocyanine (CuPc) surface cells have been studied at room temperature (30 °C). The change in the conductivity of the surface type sample cells under illumination of light was studied as a function of duration and wavelength of photoexcitation. The photoconductivity spectrum of a film of CuPc surface cell does not agree with the absorption spectrum. Particularly for the photoexciting wavelengths in the region 400–500 nm, the photoconductivity shows an appreciable value (or comparatively higher value), although the absorbance in this region is minimum or very less. The change in current under illumination of light and after turning it off has indicated that photoinduced effects persist for a longer period of time even after turning off the illumination of light of various wavelengths and duration. An increase in persistence in photocurrent was noticed with the repeated exposure within a short interval of time. Such studies are important for searching new types of electrically conducting systems (semiconductors) in the form of nanostructured thin films for use as photoactive materials in optoelectronic and memory devices.     

Electrical conductivity studies of mixed phthalocyanine thin films

Thin films of mixed of Copper Phthalocyanine (CuPc) and Nickel Phthalocyanine (NiPc) are deposited onto a pure glass substrate by a simultaneous thermal evaporation technique at room temperature. The material D.C. electrical conductivity of films at room temperature and also films annealed at 523 K has been investigated. The optical absorption and band gaps of the films are also measured. The results show that the electrical resistance is lower for the mixed films compared with the pure samples and also the optical band gap decreases for the mixed samples compared to the pure samples.     

A scanning tunneling microscopy study on the effect of post-deposition annealing of copper phthalocyanine thin films

Using scanning tunneling microscopy, overlayer lattice structures and thin film morphology of copper phthalocyanine (CuPc) have been investigated while varying posterior, annealing temperatures. The room temperature deposition of CuPc on Ag(1 1 1) resulted in ordered domains, which were three molecular layers high and separated with disordered regions. The ordered surface also exhibited an oblique lattice with the lattice constants of 13.3 Å and 16.4 Å and the angle of 74° between the two. By annealing the thin films systematically to 580 K, the symmetry of overlayer lattice increased from the oblique to the square lattice, commonly observed on various substrates. Further annealing to 780 K desorbed much of the CuPc molecules. However, the remaining molecules reacted and formed dendrite-like chains, in which each CuPc molecule was linked through its isoindole rings. A possible model for the formation of dendritic chains through polymerization is discussed.     

Morphological and optical characterization of thermally evaporated copper sulphide thin films

Thin films of Cu₂S on opaque gold layers and quartz substrates at the temperature of 393 K were deposited by a thermal evaporation technique. The surface morphology of the Cu₂S thin films at different thicknesses is investigated by AFM. It is seen that all the films are composed of highly coordinated spherical nano-sized particles well adhered to the substrate. The transmittance and reflectance spectra of Cu₂S thin films on the quartz substrate were recorded by a UV–visible spectrophotometer. The results show that the thermally evaporated Cu₂S thin films have the characteristic transmittance and reflectance suitable for optoelectronic applications. The stoichiometry and surface morphology of a grown Cu₂S thin film were confirmed by energy-dispersive X-ray spectroscopy (EDAX) and scanning electron microscopy (SEM), respectively. The dependence of the refractive index and the extinction coefficient on the photon energy for both the surface film and the opaque gold layer have been determined by ellipsometry. From the spectral behaviour of the absorption coefficient at two distinct absorption regions, a dual-band scheme of optical absorption for a Cu₂S thin film is described. The indirect and direct edges of Cu₂S are found to be about at 0.91 eV and 2.68 eV, respectively.     

Aluminium phthalocyanine chloride thin films for temperature sensing

This study presents the fabrication and temperature sensing properties of sensors based on aluminium phthalocyanine chloride(AlPcCl)thin films.To fabricate the sensors,50-nm-thick electrodes with 50-μm gaps between them are deposited on glass substrates.AlPcCl thin films with thickness of 50–100 nm are deposited in the gap between electrodes by thermal evaporation.The resistance of the sensors decreases with increasing thickness and the annealing at 100℃ results in an increase in the initial resistance of sensors up to 24%.The sensing mechanism is based on the change in resistance with temperature.For temperature varying from 25℃ to 80℃,the change in resistance is up to 60%.Simulation is carried out and results obtained coincide with experimental data with an error of±1%.     

Optical characterization of antimony-based bismuth-doped thin films with different annealing temperatures

Antimony-based bismuth-doped thin film,a new kind of super-resolution mask layer,is prepared by magnetron sputtering.The structures and optical constants of the thin films before and after annealing are examined in detail.The as-deposited film is mainly in an amorphous state.After annealing at 170-370℃,it is converted to the rhombohedral-type of structure.The extent of crystallization increased with the annealing temperature.When the thin film is annealed,its refractive index decreased in the most visible region,whereas the extinction coefficient and reflectivity are markedly increased.The results indicate that the optical parameters of the film strongly depend on its microstructure and the bonding of the atoms.     

Morphological control of copper phthalocyanine films by protonation-electrophoretic deposition

Films composed of various nanostructured copper phthalocyanine are controllably prepared by the method of protonation-electrophoretic deposition. The ultralong nanowires of copper phthalocyanine are grown at the deposition temperature of 70 °C. And the results of films UV-vis absorption spectra and X-ray diffraction indicate that copper phthalocyanine possesses the transformation tendency from α-phase to thermostable β-phase under the higher deposition temperature. The formation process of the ultralong nanowires illustrates that the nanowires grow in longitudinal orientation much faster than in lateral direction. And the time dependence of the films morphology, from another point of view, proves that copper phthalocyanine is dissolved in the precursor solutions, and the formation of the nanostructured copper phthalocyanine contains the process of crystal growth, which is different from the traditional electrophoretic deposition. So the films morphology is flexible to be controlled by varying the deposition conditions. These diverse nanostructured films have potential applications in the electrochemical and optoelectrical equipments.     

Ferroelectric phase transition in Langmuir-Blodgett films of copper phthalocyanine

A ferroelectric phase transition is observed in Langmuir-Blodgett films prepared from substituted copper phthalocyanine molecules. The linear and nonlinear dielectric properties of the films and the switching of their spontaneous polarization are investigated in the temperature range of the phase transition. The observed features can be explained by the Landau-Ginzburg model of a first-order phase transition. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 9, 625–631 (10 November 1999)